Water-induced isomerism of salicylaldehyde and 2-acetylpyridine mono- and bis-(thiocarbohydrazones) improves the antioxidant activity: spectroscopic and DFT study
Само за регистроване кориснике
2019
Аутори
Assaleh, Mohamed H.Božić, Aleksandra R.
Bjelogrlić, Snežana K.
Milošević, Milena D.
Simić, Milena R.
Marinković, Aleksandar
Cvijetić, Ilija
Чланак у часопису (Објављена верзија)
Метаподаци
Приказ свих података о документуАпстракт
Thiocarbohydrazones (TCHs) and structurally related molecules are versatile organic compounds which exert antioxidant, anticancer, and other beneficial health effects. The combination of UV/Vis, NMR spectroscopy, and quantum chemical calculations was used to rationalize the experimentally observed increase in the radical scavenging activity upon the addition of water in DMSO solution of TCHs. Mono- and bis(salicylaldehyde) TCHs (compounds 1 and 2) undergo water-induced E-to-Z isomerization which is followed by disruption of intramolecular hydrogen bond, ground state destabilization, and 11 kcal/mol decrease in the bond dissociation enthalpy (BDE). Electron spin delocalization is more pronounced in Z-isomers of 1 and 2. On the other hand, 2-acetylpyridine TCHs (compounds 3 and 4) undergo thione-to-thiol tautomerism which also decreases the BDE and facilitates the hydrogen atom transfer to 2,2-diphenyl-1-picrylhydrazyl radical (DPPH.). The appearance of thiolic -SH group as another react...ive site toward free radicals improves the antioxidant activity of 3 and 4. The spin density of 3- and 4-thiol radicals is delocalized over the entire thiocarbohydrazide moiety compared to more localized spin of thione radicals. Additional stabilization of thiol radicals corroborates with the increased antioxidant activity. This study provides the new insights on the solution structure of TCHs, and also highlights the importance of solution structure determination when studying the structure-antioxidant relationships of isomerizable compounds.
Кључне речи:
Thiocarbohydrazones / E / Z isomerism / Tautomerism / Antioxidant activity / Bond dissociation enthalpy / Spin density distributionИзвор:
Structural Chemistry, 2019, 30, 6, 2447-2457Издавач:
- Springer/Plenum Publishers, New York
Финансирање / пројекти:
- Проучавање синтезе, структуре и активности органских једињења природног и синтетског порекла (RS-MESTD-Basic Research (BR or ON)-172013)
- Рационални дизајн и синтеза биолошки активних и координационих једињења и функционалних материјала, релевантних у (био)нанотехнологији (RS-MESTD-Basic Research (BR or ON)-172035)
- Интеракције природних производа, њихових деривата и комплексних једињења са протеинима и нуклеинским киселинама (RS-MESTD-Basic Research (BR or ON)-172055)
DOI: 10.1007/s11224-019-01371-4
ISSN: 1040-0400
WoS: 000494698700034
Scopus: 2-s2.0-85068185532
Институција/група
Tehnološko-metalurški fakultetTY - JOUR AU - Assaleh, Mohamed H. AU - Božić, Aleksandra R. AU - Bjelogrlić, Snežana K. AU - Milošević, Milena D. AU - Simić, Milena R. AU - Marinković, Aleksandar AU - Cvijetić, Ilija PY - 2019 UR - http://TechnoRep.tmf.bg.ac.rs/handle/123456789/4147 AB - Thiocarbohydrazones (TCHs) and structurally related molecules are versatile organic compounds which exert antioxidant, anticancer, and other beneficial health effects. The combination of UV/Vis, NMR spectroscopy, and quantum chemical calculations was used to rationalize the experimentally observed increase in the radical scavenging activity upon the addition of water in DMSO solution of TCHs. Mono- and bis(salicylaldehyde) TCHs (compounds 1 and 2) undergo water-induced E-to-Z isomerization which is followed by disruption of intramolecular hydrogen bond, ground state destabilization, and 11 kcal/mol decrease in the bond dissociation enthalpy (BDE). Electron spin delocalization is more pronounced in Z-isomers of 1 and 2. On the other hand, 2-acetylpyridine TCHs (compounds 3 and 4) undergo thione-to-thiol tautomerism which also decreases the BDE and facilitates the hydrogen atom transfer to 2,2-diphenyl-1-picrylhydrazyl radical (DPPH.). The appearance of thiolic -SH group as another reactive site toward free radicals improves the antioxidant activity of 3 and 4. The spin density of 3- and 4-thiol radicals is delocalized over the entire thiocarbohydrazide moiety compared to more localized spin of thione radicals. Additional stabilization of thiol radicals corroborates with the increased antioxidant activity. This study provides the new insights on the solution structure of TCHs, and also highlights the importance of solution structure determination when studying the structure-antioxidant relationships of isomerizable compounds. PB - Springer/Plenum Publishers, New York T2 - Structural Chemistry T1 - Water-induced isomerism of salicylaldehyde and 2-acetylpyridine mono- and bis-(thiocarbohydrazones) improves the antioxidant activity: spectroscopic and DFT study EP - 2457 IS - 6 SP - 2447 VL - 30 DO - 10.1007/s11224-019-01371-4 ER -
@article{ author = "Assaleh, Mohamed H. and Božić, Aleksandra R. and Bjelogrlić, Snežana K. and Milošević, Milena D. and Simić, Milena R. and Marinković, Aleksandar and Cvijetić, Ilija", year = "2019", abstract = "Thiocarbohydrazones (TCHs) and structurally related molecules are versatile organic compounds which exert antioxidant, anticancer, and other beneficial health effects. The combination of UV/Vis, NMR spectroscopy, and quantum chemical calculations was used to rationalize the experimentally observed increase in the radical scavenging activity upon the addition of water in DMSO solution of TCHs. Mono- and bis(salicylaldehyde) TCHs (compounds 1 and 2) undergo water-induced E-to-Z isomerization which is followed by disruption of intramolecular hydrogen bond, ground state destabilization, and 11 kcal/mol decrease in the bond dissociation enthalpy (BDE). Electron spin delocalization is more pronounced in Z-isomers of 1 and 2. On the other hand, 2-acetylpyridine TCHs (compounds 3 and 4) undergo thione-to-thiol tautomerism which also decreases the BDE and facilitates the hydrogen atom transfer to 2,2-diphenyl-1-picrylhydrazyl radical (DPPH.). The appearance of thiolic -SH group as another reactive site toward free radicals improves the antioxidant activity of 3 and 4. The spin density of 3- and 4-thiol radicals is delocalized over the entire thiocarbohydrazide moiety compared to more localized spin of thione radicals. Additional stabilization of thiol radicals corroborates with the increased antioxidant activity. This study provides the new insights on the solution structure of TCHs, and also highlights the importance of solution structure determination when studying the structure-antioxidant relationships of isomerizable compounds.", publisher = "Springer/Plenum Publishers, New York", journal = "Structural Chemistry", title = "Water-induced isomerism of salicylaldehyde and 2-acetylpyridine mono- and bis-(thiocarbohydrazones) improves the antioxidant activity: spectroscopic and DFT study", pages = "2457-2447", number = "6", volume = "30", doi = "10.1007/s11224-019-01371-4" }
Assaleh, M. H., Božić, A. R., Bjelogrlić, S. K., Milošević, M. D., Simić, M. R., Marinković, A.,& Cvijetić, I.. (2019). Water-induced isomerism of salicylaldehyde and 2-acetylpyridine mono- and bis-(thiocarbohydrazones) improves the antioxidant activity: spectroscopic and DFT study. in Structural Chemistry Springer/Plenum Publishers, New York., 30(6), 2447-2457. https://doi.org/10.1007/s11224-019-01371-4
Assaleh MH, Božić AR, Bjelogrlić SK, Milošević MD, Simić MR, Marinković A, Cvijetić I. Water-induced isomerism of salicylaldehyde and 2-acetylpyridine mono- and bis-(thiocarbohydrazones) improves the antioxidant activity: spectroscopic and DFT study. in Structural Chemistry. 2019;30(6):2447-2457. doi:10.1007/s11224-019-01371-4 .
Assaleh, Mohamed H., Božić, Aleksandra R., Bjelogrlić, Snežana K., Milošević, Milena D., Simić, Milena R., Marinković, Aleksandar, Cvijetić, Ilija, "Water-induced isomerism of salicylaldehyde and 2-acetylpyridine mono- and bis-(thiocarbohydrazones) improves the antioxidant activity: spectroscopic and DFT study" in Structural Chemistry, 30, no. 6 (2019):2447-2457, https://doi.org/10.1007/s11224-019-01371-4 . .